CN103755854A - Preparation method of branched poly (p-hydroxystyrene) - Google Patents
Preparation method of branched poly (p-hydroxystyrene) Download PDFInfo
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- CN103755854A CN103755854A CN201310751967.9A CN201310751967A CN103755854A CN 103755854 A CN103755854 A CN 103755854A CN 201310751967 A CN201310751967 A CN 201310751967A CN 103755854 A CN103755854 A CN 103755854A
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Abstract
The invention discloses a preparation method of branched poly (p-hydroxystyrene). The preparation method comprises the steps: firstly, through simple free radical polymerization, with ethenylphenol acetate as a polymerization unit and vinyl benzyl mercaptane as a chain transfer monomer, preparing branched poly(p-ethenylphenol acetate) in a tetrahydrofuran solution, and then performing deacetoxylation on the branched poly(p-ethenylphenol acetate) to prepare the branched poly (p-hydroxystyrene). The polymerization process is easy to control and is capable of controlling the molecular weight of a polymer through adjusting the reaction time and the content of the chain transfer monomer.
Description
Technical field
The present invention relates to a kind of preparation method of branching type poly(4-hydroxystyrene), affiliated polymeric material field.
Background technology
The aspects such as poly(4-hydroxystyrene) is widely used in being combined to, phase-transfer catalysis and the same phasing of HPLC, epoxy resin anabolica, organic liquid waste sorbent material, selectively permeable membrane, radical scavenger and oxidation inhibitor, more because poly(4-hydroxystyrene) is optical clear at 248nm place, and there are good caustic solubility and excellent anti-dry etching ability, become the primary selection of 248nm photo-resist film-forming resin.
With the linear polymer phase ratio of tradition, branching type polymkeric substance due between its highly branched structure, molecule without tangle, have a large amount of can reactive behavior end group etc. feature, there is the features such as low viscosity, high-density and good solubility energy and film forming properties.
At present for the poly(4-hydroxystyrene) of 248nm photo-resist, mostly be line style, branching type poly(4-hydroxystyrene) rarely has report in the application of 248nm photo-resist.
Summary of the invention
For existing problem, the present invention has synthesized a kind of branching type poly(4-hydroxystyrene).First, utilize to vinyl benzyl mercaptan is shifted monomer, to acetoxy-styrene, is polymerization main monomer for chain, with the sulfydryl chain transfer method of free radical thermal-initiated polymerization, prepare branching type poly-to acetoxy-styrene.Then by the poly-poly(4-hydroxystyrene) that thereby the desacetoxy of acetoxy-styrene is obtained to branching type.
A kind of preparation method of branching type poly(4-hydroxystyrene) is as follows:
(1) will be to vinyl benzyl mercaptan under condition of normal pressure, acetoxy-styrene and radical polymerization initiator are dissolved in polymer solvent;
(2) under whipped state, by step (1) gained solution be heated to 30～40 ℃ and wherein logical nitrogen to make in reaction vessel be nitrogen atmosphere, sealed reaction vessel, is keeping solution temperature being risen to insulation reaction 10～24h at 65～80 ℃ under whipped state;
(3) after reaction finishes, step (2) gained solution is added drop-wise to and in precipitation agent, carries out sedimentation and process and suction filtration, gained solid after filter is dissolved in to organic solvent again, repeated precipitation, suction filtration are processed 3 times, 30 ℃ of vacuum-dryings, to constant weight, obtain product branching type poly-to acetoxy-styrene;
(4) in flask with three necks,round bottom, add step (3) products therefrom and organic solvent; under nitrogen protection; in flask, drip certain density ammoniacal liquor; under magnetic agitation in 50～80 ℃ of oil bath insulation reaction 24h; cool to room temperature adds a large amount of hydrochloric acid to solution to be acid in flask.Gained solution is added drop-wise in precipitation agent and carries out sedimentation processing suction filtration, gained solid after filter is dissolved in to organic solvent again, repeated precipitation, suction filtration are processed 3 times, and 30 ℃ of vacuum-dryings, to constant weight, finally obtain branching type poly(4-hydroxystyrene).
Radical polymerization initiator described in step (1) is azobisisobutyronitrile (AIBN), and described polymer solvent is tetrahydrofuran (THF);
Described in step (1) to the molar weight of vinyl benzyl mercaptan be to acetoxy-styrene amount 2%～10%.
Radical polymerization initiator content described in step (1) be to acetoxy-styrene and to vinyl benzyl mercaptan total mass 2%～9%.
Described in step (1), to acetoxy-styrene, total mass to vinyl benzyl mercaptan and the mass ratio of polymer solvent, be 1: 8～30.
Described in step (3), organic solvent is tetrahydrofuran (THF), and described precipitation agent is methyl alcohol.
Described in step (4), organic solvent is methyl alcohol, and described precipitation agent is deionized water.
In step (4), the mass ratio of poly-acetoxy-styrene and methyl alcohol is 1: 10～20.
In step (4), ammonium hydroxide concentration used is 28～30wt%, and used salt acid concentration is 5～10wt%.
In step (4), the mass ratio of poly-acetoxy-styrene and ammoniacal liquor is 1: 1～5.
Branching type poly(4-hydroxystyrene) of the present invention, its preparation be take to vinyl benzyl mercaptan as chain shift monomer, take acetoxy-styrene as polymkeric substance main monomer, take tetrahydrofuran (THF) as polymer solvent, take AIBN as initiator, prepare branching type poly-to acetoxy-styrene, thereby then by branching type, gather the poly(4-hydroxystyrene) that the desacetoxy of acetoxy-styrene is obtained to branching type.By regulating the degree of branching and the mechanical and physical performance thereof that mole charging capacity of vinyl benzyl mercaptan are regulated to resulting polymers.Controlled, the excellent performance of branching type poly(4-hydroxystyrene) polymerizing condition gentleness, structure properties, preparation manipulation that the present invention proposes are easy.
Accompanying drawing explanation:
Fig. 1 is reaction mechanism of the present invention.
Fig. 2 is the poly-infrared spectra spectrogram to acetoxy-styrene and poly(4-hydroxystyrene) of this branching type.
Embodiment
In order to explain better, below in conjunction with specific embodiment, the present invention is further explained in detail the present invention, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) poly-synthetic to acetoxy-styrene of branching type: in the 100ml four-hole round-bottomed flask that thermometer, reflux condensing tube, agitator are housed, add successively (22mmol) 3.58g to acetoxy-styrene, (0.44mmol) 0.08g to vinyl benzyl mercaptan, (0.44mol) 0.072g AIBN, the tetrahydrofuran (THF) that adds again 40ml is polymer solvent, flask is placed in to thermostatical oil bath, heated and stirred to 40 ℃, closed system after logical nitrogen 10min, be warming up to 65 ℃, constant temperature stirring reaction 24h, cool to room temperature.Resulting polymers solution is added dropwise in methyl alcohol and carries out sedimentation suction filtration, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying, gained solid, through vacuum-drying, is obtained to branching type poly-to acetoxy-styrene product.
(2) the poly-desacetoxy to acetoxy-styrene of branching type: add 1.5g branching type poly-to acetoxy-styrene and 35ml methyl alcohol in 100ml there-necked flask; under nitrogen protection; to the 7.45g ammoniacal liquor dripping in flask (containing 3g ammonium hydroxide and 4.4g deionized water); under magnetic agitation in 80 ℃ of oil bath insulation reaction 24h; cool to room temperature, adds excessive hydrochloric acid to solution to be acid.Sedimentation in deionized water, dissolves gained solid after suction filtration, precipitation, purifying repeatedly.30 ℃ of vacuum-dryings, to constant weight, obtain the poly(4-hydroxystyrene) of branching type.
Embodiment 2
(1) poly-synthetic to acetoxy-styrene of branching type: in the 100ml four-hole round-bottomed flask that thermometer, reflux condensing tube, agitator are housed, add successively (22mmol) 3.58g to acetoxy-styrene, (0.88mmol) 0.16g to vinyl benzyl mercaptan, (0.44mol) 0.072g AIBN, the tetrahydrofuran (THF) that adds again 40ml is polymer solvent, flask is placed in to thermostatical oil bath, heated and stirred to 40 ℃, closed system after logical nitrogen 10min, be warming up to 65 ℃, constant temperature stirring reaction 24h, cool to room temperature.Resulting polymers solution is added dropwise in methyl alcohol and carries out sedimentation suction filtration, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying, gained solid, through vacuum-drying, is obtained to branching type poly-to acetoxy-styrene product.
(2) the poly-desacetoxy to acetoxy-styrene of branching type: add 1.5g branching type poly-to acetoxy-styrene and 35ml methyl alcohol in 100ml there-necked flask; under nitrogen protection; to the 7.45g ammoniacal liquor dripping in flask (containing 3g ammonium hydroxide and 4.4g deionized water); under magnetic agitation in 80 ℃ of oil bath insulation reaction 24h; cool to room temperature, adds excessive hydrochloric acid to solution to be acid.In deionized water, middle sedimentation, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying.30 ℃ of vacuum-dryings, to constant weight, obtain the poly(4-hydroxystyrene) of branching type.
Embodiment 3
(1) poly-synthetic to acetoxy-styrene of branching type: in the 100ml four-hole round-bottomed flask that thermometer, reflux condensing tube, agitator are housed, add successively (22mmol) 3.58g to acetoxy-styrene, (1.32mmol) 0.24g to vinyl benzyl mercaptan, (0.44mol) 0.072g AIBN, the tetrahydrofuran (THF) that adds again 40ml is polymer solvent, flask is placed in to thermostatical oil bath, heated and stirred to 40 ℃, closed system after logical nitrogen 10min, be warming up to 65 ℃, constant temperature stirring reaction 24h, cool to room temperature.Resulting polymers solution is added dropwise in methyl alcohol and carries out sedimentation suction filtration, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying, gained solid, through vacuum-drying, is obtained to branching type poly-to acetoxy-styrene product.
(2) the poly-desacetoxy to acetoxy-styrene of branching type: add 1.5g branching type poly-to acetoxy-styrene and 35ml methyl alcohol in 100ml there-necked flask; under nitrogen protection; to the 7.45g ammoniacal liquor dripping in flask (containing 3g ammonium hydroxide and 4.4g deionized water); under magnetic agitation in 80 ℃ of oil bath insulation reaction 24h; cool to room temperature, adds excessive hydrochloric acid to solution to be acid.Sedimentation in deionized water, filters, and after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying.30 ℃ of vacuum-dryings, to constant weight, obtain the poly(4-hydroxystyrene) of branching type.
Embodiment 4
(1) poly-synthetic to acetoxy-styrene of branching type: in the 100ml four-hole round-bottomed flask that thermometer, reflux condensing tube, agitator are housed, add successively (22mmol) 3.58g to acetoxy-styrene, (1.76mmol) 0.32g to vinyl benzyl mercaptan, (0.44mol) 0.072g AIBN, the tetrahydrofuran (THF) that adds again 40ml is polymer solvent, flask is placed in to thermostatical oil bath, heated and stirred to 40 ℃, closed system after logical nitrogen 10min, be warming up to 65 ℃, constant temperature stirring reaction 24h, cool to room temperature.
(2) the poly-desacetoxy to acetoxy-styrene of branching type: resulting polymers solution is added dropwise in methyl alcohol and is precipitated and suction filtration, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying, gained solid, through vacuum-drying, is obtained to branching type poly-to acetoxy-styrene product.In 100ml there-necked flask, add 1.5g branching type poly-to acetoxy-styrene and 35ml methyl alcohol; under nitrogen protection; to the 7.45g ammoniacal liquor dripping in flask (containing 3g ammonium hydroxide and 4.4g deionized water); under magnetic agitation in 80 ℃ of oil bath insulation reaction 24h; cool to room temperature, adds excessive hydrochloric acid to solution to be acid.In deionized water, precipitate, filter, after suction filtration, gained solid is dissolved repeatedly, precipitation, purifying.30 ℃ of vacuum-dryings, to constant weight, obtain the poly(4-hydroxystyrene) of branching type.
The branching type poly(4-hydroxystyrene) character that embodiment 1～4 obtains is as shown in table 1, and the chain dropping into when wherein sulfydryl monomer molar content is reaction beginning shifts monomer (to vinyl benzyl mercaptan) and accounts for the molar content that reacts main monomer (to acetoxy-styrene).
Table 1
Claims (10)
1. a preparation method for branching type poly(4-hydroxystyrene), is characterized in that preparation process is as follows:
(1) will be to vinyl benzyl mercaptan under condition of normal pressure, acetoxy-styrene and radical polymerization initiator are dissolved in polymer solvent;
(2) under whipped state, by step (1) gained solution be heated to 30～40 ℃ and wherein logical nitrogen to make in reaction vessel be nitrogen atmosphere, sealed reaction vessel, is keeping solution temperature being risen to insulation reaction 10～24h at 65～80 ℃ under whipped state;
(3) after reaction finishes, step (2) gained solution is added drop-wise in precipitation agent and carries out sedimentation processing suction filtration, gained solid after filter is dissolved in to organic solvent again, repeated precipitation, suction filtration are processed 3 times, 30 ℃ of vacuum-dryings, to constant weight, obtain branching type poly-to acetoxy-styrene;
(4) in flask with three necks,round bottom, add step (3) products therefrom and organic solvent; under nitrogen protection; in flask, drip certain density ammoniacal liquor; under magnetic agitation in 50～80 ℃ of oil bath insulation reaction 24h; cool to room temperature adds a large amount of hydrochloric acid to solution to be acid in flask.Gained solution is added drop-wise in precipitation agent and carries out sedimentation processing suction filtration, gained solid after filter is dissolved in to organic solvent again, repeated precipitation, suction filtration are processed 3 times, and 30 ℃ of vacuum-dryings, to constant weight, obtain branching type poly(4-hydroxystyrene).
2. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that radical polymerization initiator described in step (1) is azobisisobutyronitrile (AIBN), and described polymer solvent is tetrahydrofuran (THF).
3. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, it is characterized in that described in step (1) to the molar weight of vinyl benzyl mercaptan be to acetoxy-styrene molar weight 2～10%.
4. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, it is characterized in that radical polymerization initiator content described in step (1) be to acetoxy-styrene and to vinyl benzyl mercaptan total mass 2～9%.
5. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that described in step (1) that to acetoxy-styrene, total mass to vinyl benzyl mercaptan and the mass ratio of polymer solvent be 1: 8～20.
6. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that described in step (3), organic solvent is tetrahydrofuran (THF), and described precipitation agent is methyl alcohol.
7. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that described in step (4), organic solvent is methyl alcohol, and described precipitation agent is deionized water.
8. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that in step (4) that the mass ratio of poly-acetoxy-styrene and methyl alcohol is 1: 10～30.
9. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that in step (4), ammonium hydroxide concentration used is 28～30wt%, and used salt acid concentration is 5-10wt%.
10. the preparation method of a kind of branching type poly(4-hydroxystyrene) according to claim 1, is characterized in that in step (4) that the mass ratio of poly-acetoxy-styrene and ammoniacal liquor is 1: 1～5.
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Cited By (2)
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| CN105254791A (en) * | 2015-09-25 | 2016-01-20 | 苏州瑞红电子化学品有限公司 | Branched poly (p-hydroxystyrene) copolymer used for 248nm photoresist |
| CN105924553A (en) * | 2016-05-16 | 2016-09-07 | 张智斌 | Preparing method for polyhydroxystyrene polymer with molecular weight narrowly distributed |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254791A (en) * | 2015-09-25 | 2016-01-20 | 苏州瑞红电子化学品有限公司 | Branched poly (p-hydroxystyrene) copolymer used for 248nm photoresist |
| CN105924553A (en) * | 2016-05-16 | 2016-09-07 | 张智斌 | Preparing method for polyhydroxystyrene polymer with molecular weight narrowly distributed |
| CN105924553B (en) * | 2016-05-16 | 2018-07-20 | 张智斌 | A kind of preparation method of the polycarboxylated styrene Type of Collective object of molecular weight narrow ditribution |
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Application publication date: 20140430 |